Novel pigment colourants for the mass-colouring of synthetic materials

ABSTRACT

The present Application relates to pigment colorants of formula  
                 
 
     wherein R 1  is C 1 -C 6 alkyl, C 1 -C 6 alkoxy, phenoxy or halogen, R 2  is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, phenoxy, halogen, acylamino, —CH 2 NHacyl or the radical 
                 
 
     and R 3  is C 1 -C 6 alkyl, C 1 -C 6 alkoxy, phenoxy or halogen, the ring A may be further substituted by —SO 3   − M + , wherein M +  is a cation, and the rings B and C may be unsubstituted or further mono- or poly-substituted by halogen, hydroxy, —SH, amino, C 1 -C 6 alkylamino, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, phenoxy, acylamino, C 1 -C 6 thioalkyl or by thiophenyl, and the ring B may be substituted in the 5- or 8-position by a radical of formula  
                 
 
     (2), wherein R 1 , R 2  and R 3  are as defined above, to a process for their preparation, and to their use in the mass-coloring of synthetic materials.

[0001] The present invention relates to novel pigment colourants, totheir preparation and to their use in the mass-colouring of syntheticmaterials.

[0002] Pigment colourants and their use in the mass-colouring ofsynthetic materials are known. It has been found, however, that suchcolourants do not always fully meet the highest demands, especially inrespect of fastness to light, thermostability and/or colour strength.Accordingly, there is a need for new pigment colourants which yieldcoloured materials that are fast to light, thermostable and of goodtinctorial strength, and which exhibit good all-round properties.

[0003] Surprisingly, it has now been found that the pigment colourantsaccording to the invention meet the above-mentioned criteria to aconsiderable degree.

[0004] Accordingly, the present invention relates to pigment colourantsof formula

[0005] wherein

[0006] R₁ is C₁-C₆alkyl, C₁-C₆alkoxy, phenoxy or halogen,

[0007] R₂ is hydrogen, C₁-C₆alkyl, C₁-C₆alkoxy, phenoxy, halogen,acylamino, —CH₂NHacyl or the radical

[0008] and

[0009] R₃ is C₁-C₆alkyl, C₁-C₆alkoxy, phenoxy or halogen, the ring A maybe further substituted by —SO₃ ⁻M⁺, wherein M+is a cation, and the ringsB and C may be unsubstituted or further mono- or poly-substituted byhalogen, hydroxy, —SH, amino, C₁-C₆alkylamino, C₁-C₆alkyl, C₁-C₆alkoxy,phenoxy, acylamino, C₁-C₆thioalkyl or by thiophenyl, and the ring B maybe substituted in the 5- or 8-position by a radical of formula

[0010] wherein R₁, R₂ and R₃ are as defined above.

[0011] R₁, R₂ and R₃ as C₁-C₆alkyl are, for example, methyl, ethyl,propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, amyl,tert-amyl (1,1-dimethylpropyl), 1,1,3,3-tetramethylbutyl, hexyl,1-methylpentyl, neopentyl, cyclopentyl, cyclohexyl, as well as theassociated isomers.

[0012] R₁, R₂ and R₃ as C₁-C₄alkoxy are, for example, methoxy, ethoxy,propoxy or butoxy.

[0013] R₁, R₂ and R₃ as halogen are, for example, chlorine, bromine oriodine, and preferably chlorine.

[0014] Acyl in acylamino or in the formula —CH₂NHacyl is preferablyformyl, acetyl, chloroacetyl, acryl or propionyl.

[0015] C₁-C₆Thioalkyl as a substituent of ring B and/or C is, forexample, methylthio, ethylthio, propylthio or butylthio.

[0016] R₁ is preferably ethyl or bromine, and especially methyl.

[0017] R₂ is preferably hydrogen, ethyl, phenoxy, and especially methyl.

[0018] R₃ is preferably ethyl or bromine, and especially methyl.

[0019] The cation M⁺ is, for example, Na⁺, Li⁺, K⁺, Ca²⁺, Mg²⁺, Sr²⁺,Al³⁺ or the cation of an organic amine such as, for example,ethylenediamine, diethylenetriamine, triethanolamine,tri-isopropanolamine, cyclohexylamine, hexamethylenediamine, Rosin AmineD and Primene 81R.

[0020] Preference is given to pigment colourants of formula (1) whereinthe ring B is substituted by chlorine, and special preference is givento those wherein the ring B is unsubstituted or is substituted in the 5-or 8-position by a radical of formula

[0021] (2), wherein R₁, R₂ and R₃ have the definitions and preferredmeanings mentioned above.

[0022] Also preferred are pigment colourants of formula (1) wherein thering C is unsubstituted or is substituted by bromine.

[0023] Special preference is given to the pigment colourants of formula(1) wherein the ring B is unsubstituted or is substituted in the 5- or8-position by a radical of formula

wherein R₁, R₂ and R₃ are methyl, and the ring C is unsubstituted.

[0024] Very special preference is given to pigment colourants of formula(1) wherein the ring B is unsubstituted or is substituted in the5-position by a radical of formula

[0025] wherein R₁, R₂ and R₃ are methyl, and the ring C isunsubstituted.

[0026] The pigment colourants of formula (1) according to the inventionare prepared, for example, by reacting 1-chloro-, 1-nitro- or1-sulfo-anthraquinone with one equivalent of a compound of formula

[0027] wherein R₁, R₂ and R₃ are as defined for formula (1), in thepresence of alkali acetate, copper and/or a copper salt and optionallyin an organic solvent, or by reacting 1,5- or 1,8-dichloro-, 1,5- or1,8-dinitro- or 1,5- or 1,8-disulfo-anthraquinone with two equivalentsof a compound of formula (2a) in the presence of alkali acetate, copperand/or a copper salt and optionally in an organic solvent, and, whereappropriate, introducing further substituents into the resultingcompound according to conventional methods.

[0028] The compounds of formula (2a) are known or can be preparedaccording to known methods.

[0029] The present invention relates also to a method of preparingcoloured plastics or polymeric coloured particles, which methodcomprises mixing together a high molecular weight organic material andat least one pigment colourant of formula (1) in an amount having acolouring effect.

[0030] Colouring of high molecular weight organic substances with thepigment colourant of formula (1) is carried out, for example, by mixingsuch a pigment colourant with the substrates using rolling mills, mixingor grinding apparatuses, as a result of which the pigment colourant isdissolved or finely divided in the high molecular weight material. Thehigh molecular weight material with the admixed pigment colourant issubsequently processed by methods known per se, for example calendering,compression moulding, extrusion, coating, spinning, casting or byinjection moulding, whereby the coloured material acquires its finalform. The admixture of the pigment colourant may also be carried outimmediately prior to the actual processing step, for example bycontinuously feeding a solid pigment colourant, for example apulverulent pigment colourant, and, at the same time, a granulated orpowdered high molecular weight organic material, and optionally alsoadditional ingredients, for example additives, directly into the intakezone of an extruder, where mixing takes place immediately beforeprocessing. In general, however, it is preferred to mix the pigmentcolourant with the high molecular weight organic material beforehand,since more uniformly coloured substrates can be obtained.

[0031] In order to produce mouldings that are not rigid or to reducetheir brittleness, it is often desirable to incorporate so-calledplasticisers into the high molecular weight compounds prior to shaping.There may be used as plasticisers, for example, esters of phosphoricacid, phthalic acid or sebacic acid. In the method according to theinvention, the plasticisers may be incorporated into the polymers beforeor after the incorporation of the colourant. It is also possible, inorder to achieve different colour shades, to add to the high molecularweight organic substances, in addition to the pigment colourant offormula (1), also further pigments or other colourants in any desiredamounts, optionally together with further additional ingredients, forexample fillers or siccatives.

[0032] Preference is given to the colouring of thermoplastic plasticsespecially in the form of fibres. Preferred high molecular weightorganic materials that can be coloured according to the invention are,very generally, polymers having a dielectric constant ≧2.5, especiallypolyester, polycarbonate (PC), polystyrene (PS), polymethyl methacrylate(PMMA), polyamide, polyethylene, polypropylene, styrene/acrylonitrile(SAN) or acrylonitrile/butadiene/styrene (ABS). Special preference isgiven to polyester and polyamide. Very special preference is given tolinear aromatic polyesters, which can be obtained by polycondensation ofterephthalic acid and glycols, especially ethylene glycol, orcondensation products of terephthalic acid and1,4-bis(hydroxymethyl)cyclohexane, for example polyethyleneterephthalate (PET) or polybutylene terephthalate (PBTP); alsopolycarbonates, for example those of α,α-dimethyl-4,4-dihydroxy-diphenylmethane and phosgene, or polymers basedon polyvinyl chloride and on polyamide, for example polyamide 6 orpolyamide 6.6.

[0033] The pigment colourants according to the invention impart to theabove-mentioned materials, especially to the polyester and polyamidematerials, tinctorially strong, level colour shades which have very goodfastness properties in use, especially good fastness to light and goodthermostability.

[0034] The Examples which follow serve to illustrate the invention. Inthe Examples, unless indicated to the contrary, parts are parts byweight and percentages are percentages by weight.

[0035] Temperatures are given in degrees Celsius. The relationshipbetween parts by weight and parts by volume is the same as that betweengrams and cubic centimeters.

EXAMPLE 1

[0036] 12.1 parts by weight of 1-chloroanthraquinone are stirredtogether with 13.5 parts by weight of mesidine, 5.0 parts by weight ofpotassium acetate, 0.1 part by weight of copper and 0.1 part by weightof copper(I) chloride in 60.0 parts by weight of 1-pentanol for 6 hoursat 130° C. The reaction mixture is cooled and the precipitated productis filtered off with suction and washed with a small amount of1-pentanol, yielding 13.0 parts by weight of the colourant of formula

[0037] The colourant mass-colours polyester and polyamide in brilliant,lightfast red shades.

[0038] If in Example 1 the 13.5 parts by weight of mesidine are replacedby equivalent amounts of an amine indicated in column 3 of Table 1and/or if the 12.1 parts by weight of 1-chloro-anthraquinone arereplaced by equivalent amounts of an anthraquinone derivative indicatedin column 2 of Table 1, colourants having good properties are likewiseobtained. TABLE 1 Anthraquinone Shade on Ex. derivative Amine ColourantPES/PA 2

yellowish red 3 ″

yellowish red 4 ″

yellowish red 5 ″

yellowish red 6 ″

yellowish red 7

yellowish red 8 ″

yellowish red 9 ″

yellowish red 10 ″

yellowish red 11 ″

yellowish red

EXAMPLE 12

[0039] 12.1 parts by weight of 1 -chloroanthraquinone are stirredtogether with 12.0 parts by weight of 2,4-xylidine, 5.0 parts by weightof potassium acetate, 0.1 part by weight of copper and 0.1 part byweight of copper(I) chloride in 60.0 parts by weight of 1-pentanol for 6hours at 130° C. The reaction mixture is cooled and the precipitatedproduct is filtered off with suction and washed with a small amount of1-pentanol, yielding 13.5 parts by weight of the compound of formula

[0040] 4.5 parts by weight of bromine are added to 8.2 parts by weightof the compound of formula (4) in 100.0 parts by weight of chlorobenzeneat 35° C. Stirring is carried out for 12 hours at 35° C., the reactionproduct is filtered off with suction, and the residue is washed with asmall amount of chlorobenzene, yielding 10.0 parts by weight of thecolourant of formula

[0041] The colourant mass-colours polyester and polyamide in brilliant,lightfast red shades.

[0042] The products listed in Table 2 are prepared analogously toExample 12. TABLE 2 Anthraquinone Shade on Ex. derivative AmineColourant PES/PA 13

yellowish red 14

yellowish red 15 ″

yellowish red

EXAMPLE 16

[0043] 12.1 parts by weight of 1-chloroanthraquinone are stirredtogether with 10.7 parts by weight p-toluidine, 5.0 parts by weight ofpotassium acetate, 0.1 part by weight of copper and 0.1 part by weightof copper(I) chloride in 60.0 parts by weight of 1-pentanol for 6 hoursat 130° C. The reaction mixture is cooled and the precipitated productis filtered off with suction and washed with a small amount of1-pentanol, yielding 12.0 parts by weight of the compound of formula

[0044] 13.0 parts by weight of bromine are added to 7.8 parts by weightof the compound of formula (6) in 100.0 parts by weight of chiorobenzeneat 35° C. Stirring is carried out for 12 hours at 35° C., the reactionproduct is filtered off with suction, and the residue is washed with asmall amount of chiorobenzene, yielding 13.0 parts by weight of thecolourant of formula

[0045] The colourant mass-colours polyester and polyamide in brilliant,lightfast red shades.

[0046] The products listed in Table 3 can be obtained analogously toExample 16. TABLE 3 Anthraquinone Shade on Ex. derivative AmineColourant PES/PA 17

yellowish red 18 ″

yellowish red 19

yellowish red 20 ″

yellowish red 21 ″

yellowish red

EXAMPLE 22

[0047] 13.9 parts by weight of 1,5-dichloroanthraquinone are stirredtogether with 21.0 parts by weight of mesidine, 10.0 parts by weight ofpotassium acetate, 0.2 part by weight of copper and 0.2 part by weightof copper(I) chloride in 100.0 parts by weight of o-dichlorobenzene for6 hours at 170° C. The reaction mixture is cooled and the precipitatedproduct is filtered off with suction and washed with a small amount ofo-dichlorobenzene, yielding 19.0 parts by weight of the colourant offormula

[0048] The colourant mass-colours polyester and polyamide in brilliant,lightfast red shades.

[0049] If in Example 22 the 21.0 parts by weight of mesidine arereplaced by equivalent amounts of an amine indicated in column 3 ofTable 4 and/or if the 13.9 parts by weight of 1,5-dichloro-anthraquinoneare replaced by equivalent amounts of an anthraquinone derivativeindicated in column 2 of Table 4, colourants having good properties arelikewise obtained. TABLE 4 Anthraquinone Shade on Ex. derivative AmineColourant PES/PA 23

red 24 ″

red 25 ″

red 26 ″

red 27 ″

red 28

bluish red 30 ″

bluish red 31 ″

bluish red 32 ″

bluish red 33 ″

bluish red

EXAMPLE 34

[0050] 17.0 parts by weight of the compound according to Example 1 aredissolved in portions at 5-10° C. in 100% sulfuric acid. 7.0 parts byweight of N-hydroxymethylchloroacetamide are then added at 5-10° C.Stirring is carried out for 12 hours at 5-10° C., and the reactionmixture is poured onto ice. The precipitate is filtered off withsuction, washed neutral with water and dried, yielding 23.0 parts byweight of the colourant of formula

[0051] The colourant mass-colours polyester and polyamide in brilliant,lightfast red shades.

EXAMPLE 35

[0052] If in Example 34 the 7.0 parts by weight ofN-hydroxymethylchloroacetamide are replaced by 14.0 parts by weight ofN-hydroxymethylchloroacetamide, 29.0 parts by weight of the colourant offormula

[0053] are obtained. The colourant mass-colours polyester and polyamidein brilliant, lightfast red shades.

EXAMPLE 36

[0054] If in Example 35 the 17.0 parts by weight of the compoundaccording to Example 1 are replaced by 23.7 parts by weight of thecompound according to Example 22, 35.0 parts by weight of the colourantof formula

[0055] are obtained. The colourant mass-colours polyester and polyamidein brilliant, lightfast red shades.

[0056] The colourants listed in Table 5 are obtained analogously toExample 36. TABLE 5 Anthraquinone N-Hydroxymethyl Shade on Ex.derivative compound Colourant PES/PA 37

yellowish red 38 ″

yellowish red 39 ″

yellowish red 40 ″

yellowish red 41 ″

yellowish red 42 ″

yellowish red 43 ″

yellowish red 44

red 45

″

bluish red

EXAMPLE 46

[0057] 19.9 parts by weight of sodium thiophenolate are dissolved in225.0 parts by weight of dimethylformamide (DMF) at 25° C.; 25.7 partsby weight of 1-amino-4-chloroanthraquinone are added thereto inportions. The mixture is stirred for 20 hours at 25° C. and diluted withwater. The resulting reaction product is filtered off with suction,washed with a small amount of methanol and dried, yielding 30.0 parts byweight of the compound of formula

[0058] 16.5 parts by weight of the compound of formula (12) are boiledat reflux for 4 hours with 11.0 parts by weight of bromomesitylene, 2.5parts by weight of sodium carbonate, 0.1 part by weight of copper and0.1 part by weight of copper(I) chloride in 50.0 parts by weight ofnitrobenzene. The reaction mixture is cooled and the nitrobenzene isdistilled off with water vapour. The precipitated product is filteredoff with suction and dried, yielding 24.0 parts by weight of thecolourant of formula

[0059] The colourant mass-colours polyester and polyamide in lightfast,reddish blue shades.

[0060] The colourants listed in Table 6 are obtained analogously toExample 46. TABLE 6 Anthraquinone Shade on Ex. derivative ColourantPES/PA 47

thiophenolate

reddish blue 48

1) thiophenolate 2) mesidine

reddish blue 49

1) thiophenolate 2) mesidine

blue

EXAMPLE 50

[0061] 4.8 parts by weight of the compound of Example 22 are dissolvedin portions at 0-5° C. in 30.0 parts by weight of 5% oleum. The reactionmixture is stirred for 4 hours at 10° C. and poured into 200 parts byweight of ice. The precipitate is filtered off with suction, washed withwater, made into a slurry in 100 parts by weight of water, neutralisedwith 1.5 parts by weight of hexamethylenediamine, and filtered off withsuction again, yielding 6.6 parts by weight of the compound of formula

[0062] The colourant mass-colours polyamide in brilliant, lightfast redshades.

[0063] The colourants listed in Table 7 are obtained analogously toExample 50. TABLE 7 Anthraquinone Shade on Ex. derivative Colourant PA51

scarlet 52

bluish red

Colouring Example 1

[0064] 1200.00 g of polyester granules (PET Arnite D04-300, DSM) arepre-dried for 4 hours at 130° C. and then mixed homogeneously with 0.24g of the pigment colourant of formula

[0065] in a “Roller rack” mixing apparatus for 15 minutes at 60revolutions per minute. The homogeneous mixture is extruded in anextruder (twin screw 25 mm from Collin, D-85560 Ebersburg) having 6heating zones at a maximum temperature of 275° C., cooled with water,granulated in a granulator (Turb Etuve TE 25 from MAPAG AG, CH-3001Bern), and then dried for 4 hours at 130° C.

[0066] There are obtained red-coloured polyester granules having goodall-round properties, especially very good light fastness and hightemperature light fastness.

Colouring Example 2

[0067] 1200.00 g of polyamide 6 granules (Ultramid B3K, BASF) arepre-dried for 4 hours at 75° C. and then mixed homogeneously with 2.40 gof the pigment colourant of formula

[0068] in a “Roller rack” mixing apparatus for 15 minutes at 60revolutions per minute. The homogeneous mixture is extruded in anextruder (twin screw 25 mm from Collin, D-85560 Ebersburg) having 6heating zones at a maximum temperature of 220° C., cooled with water,granulated in a granulator (Turb Etuve TE 25 from MAPAG AG, CH-3001Bern), and then dried for 4 hours at 75° C.

[0069] There are obtained violet-red-coloured polyamide granules havinggood all-round properties, especially very good light fastness and hightemperature light fastness.

What is claimed is:
 1. A pigment colourant of formula

wherein R₁ is C₁-C₆alkyl, C₁-C₆alkoxy, phenoxy or halogen, R₂ ishydrogen, C₁-C₆alkyl, C₁-C₆alkoxy, phenoxy, halogen, acylamino,—CH₂NHacyl or the radical

and R₃ is C₁-C₆alkyl, C₁-C₆alkoxy, phenoxy or halogen, the ring A may befurther substituted by —SO₃ ⁻M⁺, wherein M⁺ is a cation, and the rings Band C may be unsubstituted or further mono- or poly-substituted byhalogen, hydroxy, —SH, amino, C₁-C₆alkylamino, C₁-C₆alkyl, C₁-C₆alkoxy,phenoxy, acylamino, C₁-C₆thioalkyl or by thiophenyl, and the ring B maybe substituted in the 5- or 8-position by a radical of formula

(2), wherein R₁, R₂ and R₃ are as defined above.
 2. A pigment colourantaccording to claim 1 of formula

wherein R₁ is C₁-C₆alkyl, C₁-C₆alkoxy, phenoxy or halogen, R₂ ishydrogen, C₁-C₆alkyl, C₁-C₆alkoxy, phenoxy, halogen, acylamino,—CH₂NHacyl or the radical

and R₃ is C₁-C₆alkyl, C₁-C₆alkoxy, phenoxy or halogen, and the rings Band C may be unsubstituted or further mono- or poly-substituted byhalogen, hydroxy, —SH, amino, C₁-C₆-alkylamino, C₁-C₆alkyl, C₁-C₆alkoxy,phenoxy, acylamino, C₁-C₆thioalkyl or by thiophenyl, and the ring B maybe substituted in the 5- or 8-position by a radical of formula

wherein R₁, R₂ and R₃ are as defined above.
 3. A pigment colourantaccording to either claim 1 or claim 2 , wherein R₁ is methyl, ethyl orbromine.
 4. A pigment colourant according to either claim 1 or claim 2 ,wherein R₂ is hydrogen, methyl, ethyl or phenoxy.
 5. A pigment colourantaccording to either claim 1 or claim 2 , wherein R₃ is methyl, ethyl orbromine.
 6. A pigment colourant according to either claim 1 or claim 2 ,wherein the ring B is unsubstituted or is substituted in the 5- or8-position by a radical of formula

wherein R₁, R₂ and R₃ are methyl, and the ring C is unsubstituted.
 7. Aprocess for the preparation of a pigment colourant of formula (1)according to claim 1 , which process comprises reacting 1-chloro-,1-nitro- or 1-sulfo-anthraquinone with one equivalent of a compound offormula

wherein R₁, R₂ and R₃ are as defined for formula (1), in the presence ofalkali acetate, copper and/or a copper salt and optionally in an organicsolvent, or reacting 1,5- or 1,8-dichloro-, 1,5- or 1,8-dinitro- or 1,5-or 1,8-disulfo-anthraquinone with two equivalents of a compound offormula (2a) in the presence of alkali acetate, copper and/or a coppersalt and optionally in an organic solvent, and, where appropriate,introducing further substituents into the resulting compound accordingto conventional methods.
 8. A method of mass-colouring syntheticmaterials, which method comprises incorporating a pigment colourant offormula (1) into the substance of such materials.
 9. The use of apigment colourant of formula (1) according to claim 1 in themass-colouring of synthetic materials.
 10. A synthetic material colouredaccording to claim 8 with a pigment colourant of formula (1) accordingto claim 1 .